Process of finishing textiles with silicone-colloidal melamine resin mixtures, composition and resultant article



United States Patent C) of Maine No Drawing. Filed Apr. 15, 1955, Ser.No. 501,741 19 Claims. (Cl. 117-139.4)

This invention relates to mixtures of organo polysiloxanes withpositively charged colloidal solutions of partially polymerizedaminotriazine-aldehyde condensation products, to the treatment oftextile materials with these mixtures and to the resulting treatedarticles.

Textile fabrics have been impregnated with melamine resin acid colloidsto provide resistance to shrinkage. However, a fairly stiff or crisphand is produced, and this is undesirable on certain types of fabricsand for certain purposes where a soft hand is sought. The action ofthese colloidal resins difiers considerably from the noncolloidalmelamine resins which are essentially of a monomeric nature. When atextile fabric is saturated with the noncolloidal resin, it appears thatthe resin particles penetrate into the interior of the individualfibers, whereas the colloidal resins seem to be deposited substantiallyentirely on the surface of the individual fibers. It is thought that theparticle size of the partially polymerized colloidal resins is too largeto permit any substantial penetration into the interior oftextile'fibers. Neither type of melamine resin finish alone has anytendency to render textile fabrics water repellent. v

The use of various polysiloxanes as waterproofing agents for textileshas been proposed, but many practical diificulties have arisen,especially in connection with the curing of the silicone resin on thefabric. For example, United States Patent No. 2,612,482 describes thetreatment of fabrics with a monomeric aminoplast and a mixture of organopolysiloxanes containing from 5 to 25% methyl hydrogen polysiloxane andcuring these treated materials at an extremely high temperature or at arelatively high temperature in combination with aging for many hours toproduce a water-repellent, crease-resistant finish. Curing such treatedmaterials by aging for prolonged periods in the air is not commerciallyfeasible because of the huge areas which would be required for thispurpose in a modern high production textile finishing plant. On theother hand, curing at relatively high temperatures is beyond thecapabilities of the drying equipment in many plants and is detrimentalto certain of the more delicate fabrics.

An object of the invention is to provide improved resinous compositions.

A further object of the invention is to provide substantially permanentwater repellency and improved dimensional stability in textile fabrics.

Another object of the invention is to provide a waterrepellent finishfor textiles which may be converted to the water-insoluble state atmoderate temperatures.

A still further object of the present invention is to provide apermanently softer hand on textile fabrics impregnated with a colloidalaminotriazine-aldehyde resin.

Still another object of this invention is to provide glazed or embossedfabrics having durable spot-resistant finishes.

Other objects and advantages of the invention will be apparent to thoseskilled in the art upon consideration of the detailed descriptionhereinbelow.

The above objects and benefits are obtained with compositions whichcomprise an aqueous dispersion of methyl hydrogen polysiloxane, apartially polymerized colloidal cationic aminotriazine-aldehydecondensation product and between about 0.5 and about 7.0 mols of an acidper mol of the condensation product on a monomeric basis. The inventionalso includes the application and conversion of these compositions tothe substantially water-insoluble state on fibrous materials and theresulting textile articles.

The compositions disclosed herein are suitable for the treatment of anyfibrous textile material. However, the effects produced vary somewhatwith the different types of textile fibers. A very high degree ofsubstantially permanent water repellency is obtained with all textiles;that is, the water-repellent characteristics of the treated article areretained to an unusually high degree after prolonged and repeatedwashing and dry cleaning operations. In addition, the hand or feel ofthe treated fabric is markedly and unexpectedly softer in all instancesthan a similar specimen of the same textile material treated withmethylated methylol melamine acid colloids alone since no additives areknown which exert a durable softening effect on finishes produced withthese colloidal resins. Improved dimensional stability is obtained withvarious fibrous textile materials upon following the treatment of thepresent invention. But again, the effect is not the same on allmaterials. A very considerable reduction in the shrinkage of cotton andviscose rayon is achieved, but this is somewhat less than the extremelyhigh reduction in'shrinkage which is produced in wool. Suitable fabricsfor application of the present treatment include cotton, linen, flax,ramie, viscose rayon, cuprammonium rayon, cellulose acetate, wool, silk,and the various synthetic materials containing linear superpolyamidessuch as nylon of both the adipamide and caprolactam types, acrylonitrilepolymers and its copolymers with vinyl acetate, methyl acrylate,2-methyl 5-vinyl pyridine, and other compatible ethylenic monomers,copolymers of vinyl chloride with vinylidene chloride, and polyesterssuch as polyethylene glycol terephthalate.

Aminotriazine containing two or three reactive amino groups such asmelamine, N-guanyl-melamine, ammeline, formoguanamine, acetoguanamine,propioguanamine, phenylguanamine, and N-alkyl-, aryl, andaralkylsubstitued derivatives thereof such as N-methylmelamine,N-phenylmelamine, N-benzylamine, etc., which contain a hydrogen atomattached to each nitrogen atom, as disclosed in United States Patent No.2,197,357, may be reacted with aldehydes to form the condensationproducts which are used for preparing the cationic colloidal resinsolutions used in the present process. Methylol melamines obtained bycondensing melamine with varying amounts of formaldehyde, i.e., in molarratios of about 1:1 to 1:20, but preferably and generally of about 1:2to 1:6, and their water-dispersible alkylated derivatives obtained byreacting the methylol melamines with lower aliphatic alcohols such asmethanol and ethanol are preferred.

Aldehydes other than the fomaldehyde of the examples, such asformaldehyde-yielding materials including paraformaldehyde andhexamethylene tetramine, benzaldehyde, furfural, acetaldehyde,paraldehyde, etc., may be used.

In general, the colloidal resin component of the present invention maybe produced in the manner described in United States Patent No.2,345,543, by aging a watersoluble noncolloidal unmethylated ormethylated methylol aminotriazine in the presence of an acid until themolecules of the aminotriazine compound polymerize sufficiently to reachcolloidal size and exhibit the characteristic Tyndall effect under theinfluence of a beam of light or a darkfield microscope. A bluish hazealso develops in a solution of this nature. When these colloidalparticles are subjected to electrophoresis, the existence of a definitepositive charge is shown by the migration of the colloidal resin towardthe cathode.

Although strong mineral acids may be employed in preparing resincolloids intended for the treatment of wool, as exemplified byhydrochloric acid, sulfuric acid, and phosphoric acid, nevertheless weakacids such as saturated aliphatic monocarboxylic acids with dissociationconstants between 1.4 10- and about 2.5 which have water solubilities ofat least about 10% are greatly preferred, especially for the treatmentof cotton and other materials which are readily attacked by strongacids. Among the recommended hydrocarbon and hydroxy hydrocarbon acidsare formic, acetic, propionic, gluconic, .glycolic and lactic acids. Toobtain the desired results, the acidshould be employed in a molar ratiobetween about 0.5 and about 7.0 mols per mol of the aminotriazinecompound on a monomeric basis. Acetic acid is preferred for the purposesince it provides excellent results at low cost, and the recommendedquantity is between about 2 and about 5 mols per mol of aminotriazinecharged.

The polysiloxane component of the compositions described herein may beeither methyl hydrogen polysiloxane or mixtures thereof with otherlinear or cyclic siloxanes, including decamethyltetrasiloxane,octamethyl- Cyclotetrasiloxane, octamethyltrisiloxane,dodecamethylpentasiloxane, tetradecamethylhexasiloxane,octaphenyltfisiloxane, decaethyltetrasiloxane, octabenzyltrisiloxane,methyltri(trimethylsiloxy)silane, symmetrical 1,3-hexaphenyl-2 dimethyltrisiloxane, symmetrical 1,3-hexar'r'iethyl-Q-diphenyl trisiloxane, and1,3-hexamethyl-2- rnetliyl-Z-phenyl trisiloxane. This material shouldcontain at least one silicon-bonded hydrogen atom per 4 silicon atoms.Numerous suitable methyl polysiloxanes are diselosed in Patnode UnitedStates Patents 2,469,888 and 2,469,890. These materials havecarbon-silicon'linkages with an average ratio of from about 1.75 toabout 3.0 and preferably from about 1.9 to 2.1 organic groups persilicon atom. Methyl hydrogen polysiloxane for the present purpose is afluid which contains between 1.0 and 1.5 methyl radicals and between0.75 and 1.25 hydrogen atoms bonded to silicon per silicon atom in thecompound and the sum of the methyl radicals and the hydrogen atomsranges from 2.0 to 2.25 per silicon atom. Compounds of this type may beproduced by the hydrolysis and condensation of methyl hydrogendichlorosilane or by cohydrolyzing and condensing that material withanother chlorosilane. Although methyl hydrogen polys'iloxan'e may be thesole silicone in the present compositions, the best results are obtainedwith a mixture comprising from 25 to 80% of methyl hydrogen polysiloxaneand the balance a methyl polysiloxane fluid containing approximately twomethyl radicals per siliconatom with a viscosity which may range as highas 100,000 centistokes. Silicon mixtures of this nature are set forth inthe Dennett Patent No. 2,588,365.

While no accelerator is required for the acidified colloidalaminotriazine resin component of the present agents, a conventionalcatalyst is necessary or at least desirable for the polysiloxanecomponent. A wide variety of such catalysts is known, including metallicsalts such as sodium aluminate, iron, cobalt, manganese, lead and zincsalts of carboxylic acids such as acetates, stearates, palmitates,arachidates, octoates, and naphthenates. In treating a textile fabric,the catalyst for the silicone may be mixed therewith in the same bath ormay be applied either before or after the pad bath treatment by sprayingor immersing the fabric in a solution or emulsion of the catalyst forthe o rgano polysiloxane. The usual amount of such catalyst is employed;that is, from about 0.5 to

5.0% of the metal component of the salt based on the weight of theorgano polysiloxane.

Thev silicone component and its catalyst are emulsified i'n'theusual'manner in water with known'a'cid-stable dispersing agents,including polyvinyl alcohol, condensates:- of nonyl phenol with ethyleneoxide, polyethylene glycol tertdodecyl thioether, Pluramine 8-100 (anonionic condensation product of fatty acids with mono-, di-, or tri--ethanolamine and many mols of ethylene oxide) and condensation productsof dimerized soya bean fatty acids;

with 273 mols of ethylene oxide to name only a few.

present treatment.

azine resin in order to avoid any tendency toward gelling the colloidwhen the aminotriazine resin concentration of The resulting mixture themixture exceeds about 8%. has ample stability for commercial purposes.

While primarily intended for the treatment of textile materials, thecompositions of the present invention are appropriate for otherpurposes, including the manufacture of strong waterproof papers suitablefor large shipping: bags, etc., and the treatment of ropes and fishnets. Such: treatment increases the .life of manila hemp and othervegetable fibers for marine use by rendering them water resistant.

The present treatment is particularly effective in pro ducingwater-repellentsoft finishes on fabrics composed.

of substantial proportions of cotton, viscose rayon, cu-- prammoniumrayon, and cellulose acetate fibers, especially where a subsequentmechanical-finishing operation is employed to glaze or emboss theimpregnated fabric in a: However, the present process may also be 'usedwith all types of fabrics including woven, knitted, felted and nonwovenoriented constructions of any textile.-

durable manner.

Although the aqueous dispersions described herein may be applied to thefabric undergoing treatment by any known method including spraying, aconventional pad bath is usually preferred. The concentration ofsilicone and colloidal melamine resin in the treating solution isdesirably between 1 and 15%, and customarily between about 4 and 10% formaximum stability. The deposit of the impregnant onthe fabric isregulated in customary manner by selection of the bath concentration andthe pressure on the squeeze rolls which remove excess solution from thefabric undergoing treatment. The deposit of silicone and.

resin on the textile material may range from 1 to 15% based on theweight of the untreated fabric, and between '4 and about 10% isrecommended for most purposes in-- cluding treating materialssubsequently subjected to mechanical finishing.

The impregnated material is dried in a single operation, except where aglazed or embossed finish is desired. An outstanding advantage of thepresent invention is the fact that the aqueous solution of the novelcompositions may be converted to the water-insoluble state by merelydrying the treated material at the relatively low temperatures which areobainable in any textile finishing plant with conventional dryingequipment. Actually, temperatures as low as 65 F. are operative; butthey are too slow for most commercial usage. This conversion ispreferably accomplished at temperatures extending from to 250 F. in from30 seconds to 30 minutes, and the range between 200- and 225 F. isespecially recommended. Higher temperatures may also be employed in thedrying apparatus ranging up to about 350 F. for conventional equipmentor up to about 900 F. for radiant-heating apq paratus. However, nobenefits appear to be gained by this more severe and costly operationwhich may result in the tendering of the fabrics, especially those of amore delicate nature.

An excellent glazed or embossed finish is readily procurable on thetreated cloth by the use of the customary embossing calender or aglazing or friction calender. Such operations are carried out with apartially dried textile material having a moisture content between 1 and30%, and the optimum range is between 4 and 12%. One or more of therolls of such calenders may be heated preferably to temperatures betweenabout 300 and about 600 F. After passage through the calender, thefabric is substantially completely dried in the manner describedhereinabove, except that less time is required in view of the lowmoisture content of the material. Other compatible textile-treatingcompositions may be employed with the mixtures described herein eitherin the same treating bath or as separate baths or sprays; for example,aluminum phosphate, titanium dioxide, silicon dioxide, and aluminumoxide.

For a better understanding of the nature and objects 6 in. The controlsare untreated fabrics which are identical of those employed in thevarious examples. The results of these tests are set forth in Tables 1and 2 below.

EXAMPLE II Using a piece of 80 x 80 cotton print cloth, Example I isduplicated in all respects except for the type of laundering operation.

EXAMPLE A The treatment of Example I is repeated using a pad bath whichconsists only of aqueous colloidal resin C diluted with an equal weightof water to produce a bath containing 5% resin solids. Another sample ofthe same rayon fabric is padded through this bath with an 80% expressionand dried in the same fashion.

EXAMPLE B Example A is repeated with the substitution of a sample of the80 x 80 cotton print cloth of Example II.

Table 1 Fabric AATCC Spray Ratings After 3 Dry Cleanings After 21 Dr:Cleanings Hand After 12 rayon Washes After one Sanforized Wash (cotton)After Int 3 tial rayon Washes Rayon Cotton. Rayon Cotton" Soft... .doStiff.-. do...

therein.

EXAMPLE I Silicone emulsion A is prepared by adding parts by weight of95% polyethylene glycol tertdodecyl thioether (reaction product of9.1l0.3 mols of ethylene oxide per mol of tertdodecyl mercaptan) toparts of water; then 70 parts of methyl hydrogen polysiloxane areemulsified therein by slow addition with vigorous stirring. Sulficientsodium bisulfate is introduced to lower the pH to 3.5.

Silicone catalyst solution B is made up by adding with moderate stirringa solution of 12.8 parts of zinc 2-ethyl hexoate (zinc octoate) in 67.2parts of mineral spirits into a solution of 5 parts by weight of 95%polyethylene glycol tertdodecyl thioether and 15 parts of water.

Colloidal melamine resin C is prepared by dissolving 100 parts of 80%aqueous methylated trimethylol melamine prepared in accordance withExample 2 of British Patent No. 566,347 in 642.4 parts of water at about85 F. with thorough stirring; then 57.6 parts of glacial acetic acid isslowly introduced with constant stirring, and the mixture is allowed toage from 12 to 16 hours at 70 to 90 F. The resulting solution contains10% resin solids by weight and may be diluted with cold water asdesired.

The pad bath is made up by adding 5.4 parts of Ernulsion A and 1.2 partsof solution B to 50 parts of solution C in 43.4 parts of water withsuitable mixing. A viscose rayon is passed through this bath withsufiicient pressure on the pad roll to give an expression (wet pickup)of 80% based on the fabric weight. The impregnated fabric is then driedfor 4% minutes in a ventilated oven maintained at 225 F. The cloth isfound to have an add-on of 3% polysiloxane and 4% of melamine resinbased on the untreated fabric weight. Shrinkage and AATCC spray rating(water-repellency) tests are made before and after washing and drycleaning the treated material.

The laundering of rayon is carried out according to test method 40-52 inthe 1952 Technical Manual and Yearbook of the American Association ofTextile Chemists and Colorists, while the washing of cotton employed insucceeding examples follows test method 14-52 there- The shrinkage testsare made after the rayon is subected to three rayon washes, andcotton issubjected to one sanforized wash.

Table 2 Percent Percent Example Fabric arp Filling Shrinkage ShrinkageControl Untreated Rayon. 13 1 Do Untreated Cotton. 5. 5 2. 5 I Rayon 6.5 1. 5 II. Cotton 2. 5 0.5

Silicone emulsion D is prepared by stirring 2.0 parts of polyvinylalcohol as an emulsifier and 8.0 parts of xylol into 50.0 parts of waterand then adding 40.0 parts of a mixture of 40 to 50% methyl hydrogenpolysiloxane and 50 to 260% dimethyl polysiloxane.

A silicone catalyst solution E is made up of 2.0 parts of Pluronic L-64(a condensate of polypropylene glycol and polyethylene glycol), 1.0 partof polyethylene glycol 600 monooleate, 22.0 parts of water and 75.0parts of a solution of zinc octoate in mineral spirits having an 8% zinccontent by weight.

Colloidal methylated trimethylol melamine resin solution F containing10% solids is prepared similarly to resin solution C, except that 24parts lactic acid are substituted for the acetic acid therein, and 676parts water are used.

EXAMPLE III A pad bath is made by stirring 5.8 parts of the siliconeemulsion D and 08 part of catalyst solution E into 53.3 parts of thecolloidal melamine resin solution F mixed with 41.1 parts of water. Afabric woven from polyethylene glycol terephthalate fibers is paddedtherethrough with the squeeze rolls adjusted to provide for anexpression of about 60% for an add-on of 3.2% of the colloidal resin and1.4% of the polysiloxane based on the dry weight of untreated fabric.The treated material is subjected to five minutes of drying in anapparatus operating at 225 F. The initial water repellency of this clothis found to be by the AATCC spray rating method; whereas an untreatedswatch of the same fabric is found to have a rating of 0. i

p of colloidal resin solution F in 50.0 parts of water.

EXAMPLE C The procedure of Example III is duplicated exactly, with thesubstitution of the same quantity on a dry basis of a non-colloidalmethylated trimethylol melamine resin in place .of the colloidal resin.Again the drypickup is 3.2% melamine resin solids and 1.4% of the organopolysiloxane. After the same heat treatment, .the treated fabric isfound to have an initial spray rating of 0.

EXAMPLE IV A treating bath is prepared from 8.8 parts of siliconeemulsion D, 1.2 parts of catalyst solution B, and 80.0 parts of thecolloidal resin solution F in 10.0 parts of water. The method of ExampleIII is followed in general, but the pad rolls are set for a dry pickupof 4.8% colloidal resin and 2.1% of the mixed polysiloxanes on adifferent fabric woven from staple fibers of a copolymer ofacrylonitrile with about 6.0% methyl acrylate. After drying, the treatedmaterial is found to have an initial AATCC spray rating of 90 incontrast to a rating of for an untreated swatch of the same fabric.

EXAMPLE V A textile treating dispersion is prepared by introducing 3parts of silicone emulsion D and 0.4 part of accelerator solution E withstirring into 100 parts of colloidal resin solution F. A woolen suitingfabric is padded through this bath with the squeeze rolls adjusted for90% expression. The impregnated fabric is dried in an oven maintained at225 F. for 9 minutes to width andpartly released in the warp. Theresulting fabric bears 9% of the colloidal aminoplast and 1.1% of theorgano polysiloxane based on the untreated fabric weight. It isdollywashed in an aqueous solution containing 0.012% sodium dodecyltoluene sulfonate and 0.024% of the reaction product of tertbutylmercaptan with about 12 mols of ethylene oxide for five minutes and thenrinsed for five minutes before drying. No softener is employed. Thetreated material is subjected to AATCC spray rating tests and also toshrinkage tests both initially and after AATCC Wool washes, as describedin AATCC tentative test method No. 41-52. The results appear in Table 3below.

EXAMPLE v1 The procedure of Example V is in all respects duplicated,except for omitting the step of dollywashing. It is found that the handof the fabric is sufficiently soft and pleasing to obviate any need fora processor rope washing step. Table 3 contains the test results.

EXAMPLE VII The same cloth is treated according to Example VI using adifferent pad bath containing 3 parts of silicone emulsion D, 0.4 partof catalyst solution E, and 50 parts The wet pickup amounts to 98% here,and the treated fabric carries 4.9% of the melamine resin and 1.2% ofmixed polysiloxanes based on the dry weight of untreated cloth. Thismaterial is also found to have a pleasant soft hand, and the shrinkagecharacteristics are set forth in Table 3 below.

EXAMPLE VIII The procedure of Example VI is repeated with another agentprepared by mixing 2.0 parts of silicone emulsion D and 0.26 part ofcatalyst solution E into 30.0 parts of colloidal resin solution F and70.0 parts of water. The resin deposited on the suiting amounts to 2.7%of the melamine acid colloid and 0.7% of the organo polysiloxanes. Thefinished material has a soft and pleasant hand. The shrinkage test datatabulated indicate that even this light treatment reduces shrinkage to aconsiderable extent.

From the results set forth in Examples VI to VIII and Table 3, it isapparent that treating textiles with compositions containing bothcolloidal aminotriazine resins and organo polysiloxanes produce not onlya high degree of water repellency and spot resistance but also excellentshrinkage control and a hand sufficiently soft to permit omitting boththe softening additive and the process wash customarily employed withmelamine acid colloid treatments.

EXAMPLE IX 'Into 40.6 parts of water and 2.5 parts of a 50% polyvinylacetate dispersion are stirred 3.6 parts of silicone emulsion A and 0.8part of catalyst solution B and 62.5 parts of colloidal melamine resinsolution C to form a pad bath. An x 80 cotton print cloth is paddedthrough the mixed resin solution with the squeeze rolls set for an 80%wet pickup. The treated cotton fabric is partially dried in equipmentmaintained at 225 F. until the moisture content is reduced to 8 to 10%.Then it is fn'ction-calendered by one pass between calender rolls withthe nip pressure maintained at. 20 tons and thetop roll heated to 350 F.One sample of the treated fabric is then dried for five minutes inequipment operating at 225 F., and another sample is subjected to a6-minute cure in an apparatus maintained at 300 F. The add-on amounts to1.6% of the polysiloxane and 4.6% melamine resin on a dry basis. Thematerial dried at 225 F. is found to have AATCC spray rating ofinitially, 70 after a Sanforized wash at F., and 80 after threedry-cleaning operations. It has an excellent durable gloss whichproduces readings of 22 initially on a 45 Hunter glossmeter and 17 aftera Sanforized wash in contrast with a reading of 3 for the untreatedfabric. Substantially identical results are obtained with the treatedcloth cured at 300 F.; hence, no advantages appear to be gained by themore severe heat treatment.

EXAMPLE X Example IX is repeated with an all viscose gabardine suitingfabric. Similar results are obtained.

EXAMPLE XI Exampe I is repeated using an aqueous colloidal dimethylolmelamine resin of equivalent resin: acid molar ratio and resin solidscontent prepared in the same manner with 60 parts of spray-drieddimethylol melamine, 43.2 parts of glacial acetic acid, and 496.8 partsof water. The results obtained in treating the same viscose rayon fabricare similar to those obtained in Example I.

While there are above disclosed only a limited-number of embodiments ofthe compositions, process, and prodnet of the invention hereinpresented, it is possible to produce still other embodiments withoutdeparting from the inventive concept herein disclosed; and it isdesired, therefore, that only such limitations be imposed on theappended claims as are stated therein or required by the prior art.

What I claim is:

1. A composition of matter which comprises an aqueous dispersion of 1part by weight of a polysiloxane including a fluid methyl hydrogenpolysiloxane having between 1.0 and 1.5 silicon-bonded methyl radicalsand between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total ofbetween 2 and 2.25 of said silicon-bonded radicals and atoms per siliconatom; between 0.5 and 14 parts of a partially polymerized colloidalcationic aminotriazinealdehyde condensation product and between about0.5 and about 7.0 mols of an acid per mol of the condensation product ona monomeric basis.

2. A composition according to claim 1 in which a hydrogen atom is linkedto at least about 25 percent of the silicon atoms.

3. A composition according to claim 1 in which the acid has adissociation constant between about 1.4 10" and about 2.5 X and isselected from the group consisting of water-soluble hydrocarbon andhydroxy hydrocarbon acids.

4. A process -for finishing textile materials which comprises applying acomposition according to claim 1 to a textile material and drying thetreated material to convert the finish to the substantiallywater-insoluble state.

5. A process for finishing textile materials which comprises applying acomposition according to claim 1 in which a hydrogen atom is linked toat least about 25 percent of the silicon atoms to a textile material anddrying the treated material to convert the finish to the substantiallywater-insoluble state.

6. A process for finishing textile materials which comprises applying toa textile material composition according to claim 1 containing an acidof the group consisting of water-soluble hydrocarbon and hydroxyhydrocarbon acids with dissociation constants between about 1.4x 10--and about 2.5x 10" and drying the treated material to convert the finishto the substantially water-insoluble state.

7. An article which comprises a textile material bearing thesubstantially water-insoluble reaction product of the composition ofclaim 1.

8. An article which comprises a textile material bearing thesubstantially water-insoluble reaction product of a compositionaccording to claim 1 in which a hydrogen atom is linked to at leastabout 25 percent of the silicon atoms.

9. A composition of matter which comprises an aqueous dispersion of 1part by weight of a polysiloxane including a fluid methyl hydrogenpolysiloxane having between l.0 and 1.5 silicon-bonded methyl radicalsand between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total ofbetween 2 and 2.25 of said silicon-bonded radicals and atoms per siliconatom; between 0.5 and 14 parts of a partially polymerized colloidalcationic methylated methylol melamine and between about 0.5 and about7.0 mols of a water-soluble acid per mol of methylated methylol melamineon a monomeric basis, said acid having a dissociation constant betweenabout 1.4 10"' and about 2.5 1O" and being selected from the groupconsisting of hydrocarbon and hydroxy hydrocarbon acids.

10. A process for finishing textile materials which comprises applying acomposition according to claim 9 to a textile material and drying thetreated material to convert the finish to the substantiallywater-insoluble state.

11. An article which comprises a textile material bearing thesubstantially water-insoluble reaction product of a compositionaccording to claim 9.

12. A composition of matter which comprises an aqueous dispersion of 1part by weight of a polysiloxane including a fluid methyl hydrogenpolysiloxane having between 1.0 and 1.5 silicon-bonded methyl radicalsand between 0.75 and 1.25 silicon-bonded hydrogen atoms for a total ofbetween 2 and 2.25 of said silicon-bonded radicals and atoms per siliconatom; between 0.5 and 14 parts of a partially polymerized colloidalcationic methylol melamine and between about 0.5 and about 7.0 mols of awater-soluble acid per mol of methylol melamine on a monomeric basis,said acid having a dissociation constant between about 1.4x l0- andabout 2.5 10 and being selected from the group consisting of hydrocarbonand hydroxy hydrocarbon acids.

13. A process for finishing textile materials which comprises applying acomposition according to claim 12 to a textile material and drying thetreated material to convert the finish to the substantiallywater-insoluble state.

14. An article which comprises a textile material bearing thesubstantially water-insoluble reaction product of a compositionaccording to claim 12.

15. A composition of matter which comprises an acidic aqueous dispersionof 1 part by Weight of a methyl polysilo-xane mixture containing betweenabout 25 and about percent of a fluid methyl hydrogen polysiloxanehaving between 1.0 and 1.5 silicon-bonded methyl radicals and between0.75 and 1.25 silicon-bonded hydrogen atoms for a total of between 2 and2.25 of said siliconbonded radicals and atoms per silicon atom; between0.5 and 14 parts of a partially polymerized colloidal cationicmethylated trimet-hylol melamine and between about 0.5 and about 7 molsof acetic acid per mol of the melamine ether on a monomeric basis.

16. A textile finishing process which comprises treating a textilematerial with a sufficient quantity of a composition according to claim15 to deposit a total of at least about 1 percent of the polysiloxaneand the melamine resin thereon based on the dry weight of the materialand drying the treated textile material at a temperature between aboutand about 250 degrees Fahrenheit to convert the finish to thesubstantially waterinsoluble state.

17. A textile finishing process which comprises treating a textilematerial with a sufiicient quantity of the composition of claim 15 todeposit thereon a total of between about 4 and about 10 percent based onthe weight of the dry untreated textile material, partially drying thetreated material to a moisture content between about 4 and about 12percent by weight, mechanically finishing the partially dry textilematerial under heat and pressure, and substantially completely dryingthe mechanically finished textile material to convert the finish to thesubstantially water-insoluble state.

18. An article which comprises a mechanically finished textile materialprepared according to the process of claim 17.

19. An article which comprises a textile material bearing at least about2 percent based on the weight of the dry untreated textile material ofthe substantially waterinsoluble reaction product of the composition ofclaim 15.

References Cited in the file of this patent UNITED STATES PATENTS2,121,005 Bener June 21, 1938 2,588,365 Dennett Mar. 11, 1952 2,612,482Rasmussen Sept. 30, 1952 2,661,262 Folkers Dec. 1, 1953 2,757,152Solomon July 31, 1956 2,758,946 Spalding et a1. Aug. 14, 1956

1. A COMPOSITIOIN OF MATTER WHICH COMPRISES AN AQUEOUS DISPERSION OF 1PART BY WEIGHT OF A POLYSILOXANE INCLUDING A FLUID METHYL HYDROGENPOLYSILOXANE HAVING BETWEEN 1.0 AND 1.5 SILICON-BONDED METHYL RADICALSAND BETWEEN 0.75 AND 1.25 SILICON-BONDED HYDROGEN ATOMS FOR A TOTAL OFBETWEEN 2 AND 2.25 OF SAID SILICON-BONDED RADICALS AND ATOMS PER SILICONATOM; BETWEEN 0.5 AND 14 PARTS OF A PARTIALLY POLYMERIZED COLLOIDALCATIONIC AMINOTRIAZINEALDEHYDE CONDENSATION PRODUCT AND BETWEEN ABOUT0.5 AND ABOUT 7.0 MOLS OF AN ACID PER MOL OF THE CONDENSATION PRODUCT ONA MONOMERIC BASIS.
 7. AN ARTICLE WHICH COMPRISES A TEXTILE MATERIALBEARING THE SUBSTANTIALLY WATER-INSOLUBLE REACTION PRODUCT OF THECOMPOSITION OF CLAIM 1.